EP0002204B1 - Acides alpha-phénoxy propanethioiques et leurs sels, leur préparation et leur utilisation comme herbicides ou intermédiaires - Google Patents

Acides alpha-phénoxy propanethioiques et leurs sels, leur préparation et leur utilisation comme herbicides ou intermédiaires Download PDF

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Publication number
EP0002204B1
EP0002204B1 EP78101372A EP78101372A EP0002204B1 EP 0002204 B1 EP0002204 B1 EP 0002204B1 EP 78101372 A EP78101372 A EP 78101372A EP 78101372 A EP78101372 A EP 78101372A EP 0002204 B1 EP0002204 B1 EP 0002204B1
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Prior art keywords
acid
salt
formula
phenoxy
radical
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Expired
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EP78101372A
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German (de)
English (en)
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EP0002204A1 (fr
Inventor
Beat Dr. Böhner
Otto Dr. Rohr
Hermann Dr. Rempfler
Georg Dr. Pissiotas
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids

Definitions

  • the present invention relates to new herbicidally active, para-substituted x-phenoxypropionethiol acids and their salts, processes for their preparation, further herbicidal compositions which contain these new compounds as active compounds, and processes for controlling weeds using the new acids and Salts or the compositions containing them, and the use of these compounds as intermediates for the synthesis of further herbicidally active derivatives
  • Substituents of a phenyl radical Z are one or two from the group halogen, CF 3 , cyano and nitro.
  • Substituents of a pyridyl (2) radical Z are halogen and trifluoromethyl
  • alkali and alkaline earth metal ions and the ions of the metals Fe, Cu, Zn, Mn and Ni are primarily considered.
  • Polyvalent cations of the valency n are equivalent bound as radical R with the rest of the acid.
  • halogen substituents bromine and especially chlorine are preferred.
  • the acids of the formula I and salts thereof can also be used as intermediates for the synthesis of others highly effective herbicides, namely corresponding thiolic acid derivatives such as esters, amides, etc. can be used.
  • a process for the preparation of the new substituted ⁇ -phenoxy-propionthiol acids and their salts of the formula I is characterized in that an ⁇ -phenoxy-propionic acid halide of the formula 11 in which Z has the meaning given under formula 1 and Hal represents a halogen atom, in particular chlorine, in the presence of a basic acid acceptor with hydrogen sulfide or one of its salts and isolates the resulting thiolic acid salt or by acidifying the thiolic acid itself and optionally in and transferred a salt.
  • the reaction is preferably carried out in a solvent which is inert to the reaction components.
  • Suitable solvents are those from a wide variety of substance classes, such as aliphatic and aromatic hydrocarbons and preferably polar organic solvents, such as alcohols, ethers, ketones, amides, stable esters, e.g. B. methyl ethyl ketone, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran.
  • an organic base (amine) such as pyridine can also be used as the solvent, which then also acts as the acid acceptor and of course the corresponding salt of the thiolpropionic acid formed is already formed in the reaction mixture.
  • aqueous alkali metal hydroxides such as KOH and NaOH as well as other common basic substances such as ammonia, carbonates (K 2 C0 3 , NaHC0 3 ), alcoholates (NaOCH s and potassium tert.butylate), but also organic bases such as triethylamine etc . be used. If an organic base (e.g. pyridine) serves as a solvent, it also fulfills the function of the acid acceptor.
  • organic base e.g. pyridine
  • a sulfide or hydrogen sulfide such as, for. B.
  • a mineral acid such as conc. Hydrochloric acid and adjust to a pH of about 1.
  • the starting materials of the formula 11, in particular the x-phenoxypropionic acid chlorides, can best be prepared from the corresponding free propionic acids by reaction with thionyl chloride SOCl 2 in a known manner.
  • the free nucleus-substituted x-phenoxy-propionic acids are known compounds which have been described, inter alia, in DE-OS 2 223 894, 2 531 643, 2 546 251, 2 433 067 and 2 652 384.
  • the preparation of the thiol acids of the formula I mostly amounts to the replacement of the hydroxyl group in oxygen acids by the HS group, for which further process variants are possible, which are described in "Houben-Weyl", Volume VIII, pages 480 and 481 (1952) are. It is an acylation of hydrogen sulfide.
  • the new thiol acids and salts of the formula are also important intermediates for the preparation of corresponding propionthiolic acid esters with herbicidal activity, some of which are known and described, for example, in DE-OS 2 223 894 and 2 531 643, but have hitherto been used in a different way have been produced.
  • a new group of ⁇ - [4- (phenoxy) phenoxy] and ⁇ - [4- (pyridyloxy) phenoxy] thiolcarboxylic acid derivatives has been developed with the propionthiol acids and their salts according to the invention, which derivatives are strong at relatively low application rates Show herbicidal activity and / or can regulate plant growth in other ways that are useful for agriculture.
  • the new active compounds of the formula I can be used as herbicides in the pre-emergence process, and in particular also in the post-emergence process. Their action is directed primarily against monocotyledon weeds, but they can also be used to inhibit growth in dicotyledonous plants.
  • the active ingredients of Formula 1 are not very toxic to warm-blooded animals; the application rates are advantageously between 0.1 and 5 kg of active ingredient per hectare.
  • the present invention also relates to herbicidal and plant growth-regulating compositions which comprise a compound of the formula I as an active component.
  • Such agents can be present in the customary manner as solid formulations (dusts, scattering agents, granules), as water-dispersible concentrates (wettable powders, emulsions, emulsion concentrates and pastes) or as solutions and are formulated according to known techniques with appropriate additives and carriers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

1. Nouveaux acides α-phénoxy-propanethioïques et leurs sels de formule 1
Figure imgb0015
où R représente un hydrogène, l'équivalent d'un cation métallique ou l'équivalent d'un cation amine ou ammonium
Figure imgb0016
où R2 à R5 représentent indépendamment l'un de l'autre, chacun, un hydrogène, un alcoyle, un alcoyle substitué, un cycioalcoyle, un aralcoyle ou un aryle, ou bien où 2 ou 3 des radicaux R2 à R5 forment, avec l'atome d'azote, un noyau hétérocyclique saturé ou insaturé, et Z est soit un radical phényl-(1) substitué, soit un radical pyridyl-(2) substitué.
2. Acides phénoxypropanethioïques et leurs sels selon la revendication 1, caractérisés en ce que le radical phényle Z est substitué par un ou deux substituants du groupe formé par les halogènes, CF3. cyano et nitro.
3. Acides phénoxypropanethioïques et leurs sels selon la revendication 1, caractérisés en ce qu'un radical pyridyl-(2) Z porte un ou deux substituants du groupe formé par les halogènes et le trifluorométhyle (CF3).
4. Acides phénoxypropanethioïques et leurs sels selon la revendication 2, caractérisés en ce qu'un substituant est en position 4, et un autre substituant éventuel en position 2 du radical phényle.
5. Acides phénoxypropanethioïques et leurs sels selon la revendication 3, caractérisés en ce qu'un substituant est en position 5 et un autre substituant éventuel en position 3 du radical pyridyle
6. Acide x-[4-(4'-trifluorométhylphénoxy)-phénoxy]-propanethioïque et son sel de pyridinium selon la revendication 1.
7. Procédé de préparation des acides x-phénoxy-propanethioïques et de leurs sels de formule 1 selon la revendication 1, caractérisé en ce qu'on fait réagir un halogénure d'acide α-phénoxy-propioni- que de formule II
Figure imgb0017
où Z a la signification donnée sous la formule 1 et où Hal représente un atome d'halogène, en particulier de chlore, en présence d'un accepteur d'acide basique avec de l'acide sulfhydrique ou un de ses sels et en ce qu'on isole du mélange réactionnel le sel de l'acide thioïque apparu ou par acidification l'acide thioïque lui-même et en ce qu'on transforme éventuellement celuici en un sel.
8. Agent herbicide, caractérisé en ce qu'il contient comme composant efficace au moins un acide α-phénoxypropanethioique ou un de ses sels de formule 1 selon la revendication 1.
9. Application des acides x-phénoxy-propanethioiques et de leurs sels de formule 1 selon la revendication 1 comme herbicides.
EP78101372A 1977-11-24 1978-11-15 Acides alpha-phénoxy propanethioiques et leurs sels, leur préparation et leur utilisation comme herbicides ou intermédiaires Expired EP0002204B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1439877 1977-11-24
CH14398/77 1977-11-24

Publications (2)

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EP0002204A1 EP0002204A1 (fr) 1979-06-13
EP0002204B1 true EP0002204B1 (fr) 1981-09-02

Family

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Country Status (6)

Country Link
US (1) US4233060A (fr)
EP (1) EP0002204B1 (fr)
JP (1) JPS5481209A (fr)
CA (1) CA1101425A (fr)
DE (1) DE2861033D1 (fr)
IT (1) IT7830114A0 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309210A (en) * 1978-12-01 1982-01-05 Ciba-Geigy Corporation Preemergence method of selectively controlling weeds in crops of cereals and composition therefor
DE3304204A1 (de) * 1983-02-08 1984-08-09 Bayer Ag, 5090 Leverkusen Substituierte alkanthiocarbonsaeure-derivate
US4613357A (en) * 1983-04-13 1986-09-23 Stauffer Chemical Company N,N-disubstituted hydroxylamine esters of substituted pyridyloxyphenoxypropionic acids and herbicidal methods of use
JPH0715903Y2 (ja) * 1988-08-30 1995-04-12 東陶機器株式会社 衛生洗浄装置の配管接続構造
WO2003037855A1 (fr) * 2001-11-02 2003-05-08 Toray Industries, Inc. Processus de production d'acide thiocarboxylique ou de sel de celui-ci, procede de determination de purete optique de ce compose, acide tetrahydrofuranthiocarboxylique ou derive de celui-ci
MX2009008934A (es) * 2007-02-26 2009-08-28 Dow Agrosciences Llc Proceso para la preparacion de algunas sulfiliminas sustituidas.

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2259869A (en) * 1939-09-30 1941-10-21 Shell Dev Insecticide and repellent
US3165544A (en) * 1960-09-06 1965-01-12 Stauffer Chemical Co Chlorothiolformates and preparation thereof
DE2223894C3 (de) * 1972-05-17 1981-07-23 Hoechst Ag, 6000 Frankfurt Herbizide Mittel auf Basis von Phenoxycarbonsäurederivaten
DK154074C (da) * 1974-10-17 1989-02-27 Ishihara Sangyo Kaisha Alfa-(4-(5 eller 3,5 substitueret pyridyl-2-oxy)-phenoxy)-alkan-carboxylsyrer eller derivater deraf til anvendelse som herbicider, herbicidt middel samt fremgangsmaader til bekaempelse af ukrudt
CH618322A5 (fr) * 1975-08-25 1980-07-31 Ciba Geigy Ag

Also Published As

Publication number Publication date
US4233060A (en) 1980-11-11
DE2861033D1 (en) 1981-11-26
IT7830114A0 (it) 1978-11-23
EP0002204A1 (fr) 1979-06-13
JPS5481209A (en) 1979-06-28
CA1101425A (fr) 1981-05-19

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